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US3983241A - Imidazole derivatives - Google Patents

Imidazole derivatives Download PDF

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US3983241A
US3983241A US05/599,664 US59966475A US3983241A US 3983241 A US3983241 A US 3983241A US 59966475 A US59966475 A US 59966475A US 3983241 A US3983241 A US 3983241A
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compound
sub
plants
disease
fungi
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US05/599,664
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Sho Hashimoto
Akira Nakada
Saburo Kano
Susumu Takahashi
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • This invention relates to novel compounds of imidazole derivatives, to a process for the preparation thereof and their used as fungicide.
  • compositions and methods employing, as an active fungicidal ingredient, at least one compound of the formula: ##SPC2##
  • R 1 is selected from the group consisting of
  • the compound of this invention can be prepared by the following equation: ##SPC3##
  • R 1 is as previously defined.
  • 2-amino-4,5-dicyanoimidazole [II] is dissolved in an organic solvent together with a condensing agent in amounts equimolar with it and chloroformic ester [III] is added dropwise to the mixture at room temperature.
  • an organic solvent acetone, dioxane, benzene, acetonitrile, dimethylsulfoxide, dimethylformamide, preferably acetone, are used.
  • sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide and triethylamine can be used. Then, the temperature of resulting mixture is raised to 40°- 100°C and maintained at its temperature during 0.5 to 1 hour, but the reaction proceeds at a room temperature. When the reaction mixture is poured into cold water after finishing the reaction, the crystal of the crude product separates out and the crude product can be purified by recrystallization.
  • R 1 is as previously defined.
  • the above reaction can be conducted in an inert solvent such as pyridine, alkylpyridine, quinoline, alkylquinoline or isoquinoline and the reaction temperature is from room temperature to 100°C.
  • an inert solvent such as pyridine, alkylpyridine, quinoline, alkylquinoline or isoquinoline and the reaction temperature is from room temperature to 100°C.
  • the compounds of the invention control a wide variety of fingus diseases of foliage, fruit, stems and roots of growing plants without damage to the host.
  • the compounds are used for seeds dressing against helminthosporium leaf spot.
  • the compounds of the present invention have low toxicity for warm-blooded animals and fish.
  • the method of the present invention comprehends the employment of a liquid or solid composition containing one or more of the present compounds as an active component.
  • the compound can be used directly without mixing with suitable carriers.
  • the active ingredient of this invention may be formulated by mixing with suitable carriers in a form generally used in pesticidal compositions such as wet table powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol.
  • suitable carriers include wet table powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol.
  • solid carriers bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite, clay and others are used.
  • As liquid carriers kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, benzene and others are used. Sometimes surface active agent is added in order to give a homogeneous and stable formulation.
  • concentrations of the active ingredients in the fungicidal composition of this invention vary according to type of formulation and they are, for example, used in a range of 5 - 80 weight percent, preferably 20 - 80 weight percent, in wettable powders, 5 - 70 weight percent, preferably 10 - 50 weight percent, in emulsifiable concentrates, and 0.5 - 20 weight percent, preferably 1 - 10 weight percent in dust formulations.
  • wettable powder or emulsifiable concentrate containing proper quantity of the active compound is suspended or emulsified in water and then sprayed to the foliages of the plants or to the soil around the cultivated plants.
  • the compounds may be used as a mixture with other fungicides, insecticides, acaricides and herbicide.
  • wettable powder containing 40% of the active ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.
  • Apple leaves were cut off from the potted apple plant (variety: starking) and the detached leaves were immersed during 30 to 60 seconds into the diluted solution of a specified concentration of wettable powder containing test compound.
  • the leaves were inoculated with the spore suspension of Alternaria mali in the concentration of 200,000/ml and incubated in a wet chamber at 28°C.
  • the potted young apple plants (Star King) were sprayed, at a rate of 100 ml. per plant, with an aqueous suspension having a concentration of 500, 250 and 125 ppm of an active ingredient which suspension was prepared by diluting a wettable powder with water to a specified concentration.
  • Young branches having about 7 to 8 leaves were cut off from each tree and leaves were also cut off from tree after allowing to stand for 1 day, 3 days and 7 days in green-house after the spraying of above suspension, and then inoculated with spore suspension of Alternaria mali, and held under the condition of incubation for 24 hours in a wet chamber. Then, average number of lesions per branch was counted and evaluation of percent disease control was calculated on the base of number of lesions occuring on the untreated check. The state of inhibition of the spore germination was also observed.
  • Tomato leaves were cut off form the potted tomato (variety: Oogatafukuju) and the detached leaves were immersed during 30 to 60 seconds into the diluted solution of a specified concentration of wettable powder containing test compound. After air-drying, the leaves were inoculated with the zoospore suspension of late blight (Phytophthora capsici) in the concentration of 30,000/ml and incubated in a green-house at 28°C. 2 days after inoculation, the disease degree was examined and evaluation of percent disease control was calculated on the disease degree of untreated check. The results were shown in Table 4.
  • Seeds of tomato (variety: Oogatafukuju) were planted in a pot and cultivated for 2 weeks in a green-house.
  • a tomato seedling (height: 45 - 50 cm, leaves: 15 - 20) was grown in a pot.
  • tomato seedlings were inoculated with the zoospore suspension of late blight and incubated in a wet chamber at 28°C.
  • the present invention provides for a compound of the formula ##SPC5##wherein R 1 is selected from the group consisting of straight or branched chain alkyl of 1 to 12 carbon atoms, alkenyl of 3 to 4 carbon atoms, propargyl, methoxyethyl, alkyl of 2 to 4 carbon atoms substituted with one or two chlorine or bromine atoms and cyclohexyl. Within this group the invention also provides for compounds in which R 1 is alkyl of 4 to 5 carbon atoms. Compounds in which R 1 is straight or branched chain alkyl of 1 to 12 carbon atoms, lower alkenyl or lower alkynyl are also provided for in the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

This invention is directed to compositions and methods employing, as an active fungicidal ingredient, at least one compound of the formula:

Description

DETAILED DESCRIPTION OF THE INVENTION:
This invention relates to novel compounds of imidazole derivatives, to a process for the preparation thereof and their used as fungicide.
More particularly, this invention is directed to compositions and methods employing, as an active fungicidal ingredient, at least one compound of the formula: ##SPC2##
Wherein R1 is selected from the group consisting of
Straight or branched chain alkyl, lower alkenyl,
Lower alkynyl, lower alkoxyethyl, lower haloalkyl
And lower cycloalkyl.
Especially preferred for use because of their fungicidal effectiveness are:
2-amino-1-n-butoxycarbonyl-4,5-dicyanoimidazole and
2-amino-4,5-dicyano-1-n-pentyloxycarbonylimidazole.
The compound of this invention can be prepared by the following equation: ##SPC3##
Wherein R1 is as previously defined.
As a practical method of the above reaction, 2-amino-4,5-dicyanoimidazole [II] is dissolved in an organic solvent together with a condensing agent in amounts equimolar with it and chloroformic ester [III] is added dropwise to the mixture at room temperature. As an organic solvent, acetone, dioxane, benzene, acetonitrile, dimethylsulfoxide, dimethylformamide, preferably acetone, are used.
For condensing agents, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide and triethylamine can be used. Then, the temperature of resulting mixture is raised to 40°- 100°C and maintained at its temperature during 0.5 to 1 hour, but the reaction proceeds at a room temperature. When the reaction mixture is poured into cold water after finishing the reaction, the crystal of the crude product separates out and the crude product can be purified by recrystallization.
Another method of the preparation is illustrated by the following equation: ##SPC4##
Wherein R1 is as previously defined.
The above reaction can be conducted in an inert solvent such as pyridine, alkylpyridine, quinoline, alkylquinoline or isoquinoline and the reaction temperature is from room temperature to 100°C.
In order that the invention may be better understood, the following examples are given:
EXAMPLE 1. 2-amino-1-ethoxycarbonyl-4,5-dicyanoimidazole
1.33 G OF 2-AMINO-4,5-DICYANOIMIDAZOLE WAS DISSOLVED IN 10 ML OF SUSPENSION OF ACETON CONTAINING 0.7 G OF ANHYDROUS POTASSIUM CARBONATE AND THEN 1.1 G OF ETHYL CHLOROFORMATE WAS ADDED DROPWISE TO THE SOLUTION AT A ROOM TEMPERATURE.
The resulting solution was refluxed during 30 minutes, and white crystal separated out when the reaction mixture was poured into ice-water. After recrystallizing the crude product from methanol, 1.6 g of purified compound having a melting point of 195° to 197°C was obtained as needles. (Yield rate: 78% )
EXAMPLE 2. 2-amino-1-n-butoxycarbonyl-4,5-dicyanoimidazole
2 g of 2-amino-4,5-dicyanoimidazole was dissolved in 20 ml of suspension of acetone containing 1.3 g of sodium bicarbonate and then 2.1 g of n-butyl chloroformate was added dropwise to said solution at a room temperature. The resulting solution was refluxed during 30 minutes, and white crystal was separated out when the rection mixture was poured into ice-water. After recrystallizing the crude product from methanol, 2.7 g of the purified compound having a melting point of 170° to 172°C was obtained as needles (Yield rate: 77%).
EXAMPLE 3. 2-amino-4,5-dicyano-1-n-pentyloxycarbonylimidazole
2 g of 2-amino-4,5-dicyanoimidazole was dissolved in 20 ml of acetonitrile, 1.6 g of triethylamine was added to said solution and further 2.3 g of n-amyl chloroformate was added dropwise to it at a room temperature. The resulting solution was refluxed during 30 minutes, and white crystal was separated out when the reaction mixture was poured into ice-water. After recrystallizing the crude product from methanol, 3.1 g of the purified compound having a melting point of 166 to 169°C was obtained as needles (Yield rate: 83%).
EXAMPLE 4. 1-allyloxycarbonyl-2-amino-4,5-dicyanoimidazole
2 g of 2-amino-4,5-dicyanoimidazole and 2 g of allyl chloroformate were added to 20 ml of acetone and further 3 ml of water solution containing 20% of sodium hydroxide was added dropwise to it under stirring at a temperature of 15° to 20°C. After the resulting solution was stirred during an hour at a room temperature, it was poured into ice-water and thereby white crystal was separated out.
After recrystallizing the crude product from methanol, 2.3 g of the purified compound having a melting point of 186 to 188°C with decomposition was obtained as needles (Yield rate: 70%).
EXAMPLE 5. 2-amino-1-ethoxycarbonyl-4,5-dicyanoimidazole
2 g of 2-amino-4,5-dicyanoimidazole was dissolved in 20 ml of pyridine 2.5 g of diethyl pyrocarbonate was added dropwise to it and then it was stirred during two hours at a room temperature.
When the reaction mixture was poured into ice-water, white crystals were separated out. After recrystallizing the crude product from methanol, 2.1 g of the purified compound having a melting point of 195° to 197°C was obtained (Yield rate: 68%).
In addition to the above mentioned compounds described in the preceding example, some typical compounds of the present invention are listed in Table1.
                                  Table 1                                 
__________________________________________________________________________
Com-                       Elemental Analysis (%)                         
__________________________________________________________________________
pound                                                                     
No.  --R.sub.1  Physical Constant                                         
                           C       H     N                                
__________________________________________________________________________
1    --CH.sub.3 m.p. 190-191°C                                     
                           43.82*  2.89  36.48                            
                           (43.89)**                                      
                                   (2.62)                                 
                                         (36.65)                          
2    --C.sub.2 H.sub.5                                                    
                m.p. 195-197°C                                     
                           46.50   3.68  33.94                            
                           (46.83) (3.41)                                 
                                         (34.15)                          
3    --C.sub.3 H.sub.7.sup.i                                              
                m.p. 170-173°C                                     
                           49.55   4.27  32.25                            
                           (49.31) (4.11)                                 
                                         (31.96)                          
4    --C.sub.4 H.sub.9.sup.n                                              
                m.p. 170-172°C                                     
                           51.20   4.93  29.73                            
                           (51.50) (4.72)                                 
                                         (30.04)                          
5    --C.sub.4 H.sub.9.sup.i                                              
                m.p. 181-183°C                                     
                           51.72   5.03  30.18                            
                           (51.50) (4.72)                                 
                                         (30.04)                          
6    --C.sub.5 H.sub.11.sup.n                                             
                m.p. 166-169°C                                     
                           53.12   5.46  28.40                            
                           (53.44) (52.6)                                 
                                         (28.34)                          
7    --C.sub.5 H.sub.11.sup.i                                             
                m.p. 181-184°C                                     
                           53.20   5.43  28.14                            
                           (53.44) (5.26)                                 
                                         (28.34)                          
8    --C.sub.6 H.sub.13.sup.n                                             
                m.p. 163-165°C                                     
                           55.05   6.06  26.57                            
                           (55.17) (5.75)                                 
                                         (26.82)                          
9    --C.sub.7 H.sub.15.sup.n                                             
                m.p. 162-164°C                                     
                           56.58   6.03  25.22                            
                           (56.73) (6.18)                                 
                                         (25.45)                          
10   --C.sub.8 H.sub.17.sup.n                                             
                m.. 194-196°C                                      
                           58.42   6.64  24.20                            
                           (58.13) (6.57)                                 
                                         (24.23)                          
11   --CH.sub.2 CH=CH.sub.2                                               
                m.p. 186-188°C                                     
                           49.45   3.28  32.24                            
                (with decom-                                              
                           (49.77) (3.33)                                 
                                         (32.36)                          
                position)                                                 
12   --CH.sub.2 C.tbd.CH                                                  
                m.p. 201-203°C                                     
                           49.91   2.42  32.32                            
                (with decom-                                              
                           (50.23) (2.33)                                 
                                         (32.56)                          
                position)                                                 
13              m.p. 178-181°C                                     
                (with decom-                                              
                           --      --    --                               
                position)                                                 
14   --C.sub.12 H.sub.25.sup.n                                            
                m.p. 158-161°C                                     
                           --      --    --                               
15   CH.sub.3                                                             
     --CH--CH∠                                                      
                m.p. 147-149°C                                     
                           --      --    --                               
     |CH.sub.3                                                   
     CH.sub.3                                                             
16   --CH.sub.2 CH=CHCH.sub.3                                             
                m.p. 135-137°C                                     
                           --      --    --                               
17   --CH.sub.2 CHBrCHBrCH.sub.3                                          
                m.p. 168-170°C                                     
                           --      --    --                               
18   --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Cl                             
                m.p. 159-161°C                                     
                           --      --    --                               
19   --CH.sub.2 CH.sub.2 OCH.sub.3                                        
                m.p. 150-153°C                                     
                           --      --    --                               
20   --CH.sub.2 CH.sub.2 Cl                                               
                m.p. 165-168°C                                     
                           --      --    --                               
21   --CH.sub.2 CHClCH.sub.2 Cl                                           
                m.p. 169-172°C                                     
                           --      --    --                               
__________________________________________________________________________
  *Found                                                                  
 **Calculated
Hereinafter, the compounds of this invention are represented by compound No. of Table 1.
As mentioned previously, it has been found that the compound of this invention posses outstanding fungicidal activity.
The paragraphs which follow described in more detail the utility of this invention.
The compounds of the invention control a wide variety of fingus diseases of foliage, fruit, stems and roots of growing plants without damage to the host.
The many fungi against which the compounds of this invention are active may be represented by, but is not intended to be limited to, the following:
alternaria leaf spot (Alternaria mali),
black spot (Alternaria kikuchiana),
late blight (Phytophthora capsici),
crown rust (Puccinia coronate corda),
helminthosporium leaf spot (Cochliobolus miyakeanus),
downy mildew (Pseudoperonospora cubensis)
and particularly effective against alternaria leaf spot and black spot.
Further the compounds are used for seeds dressing against helminthosporium leaf spot.
It is another advantage that the compounds of the present invention have low toxicity for warm-blooded animals and fish.
The method of the present invention comprehends the employment of a liquid or solid composition containing one or more of the present compounds as an active component.
The compound can be used directly without mixing with suitable carriers. The active ingredient of this invention may be formulated by mixing with suitable carriers in a form generally used in pesticidal compositions such as wet table powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol. As solid carriers, bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite, clay and others are used. As liquid carriers, kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, benzene and others are used. Sometimes surface active agent is added in order to give a homogeneous and stable formulation.
The concentrations of the active ingredients in the fungicidal composition of this invention vary according to type of formulation and they are, for example, used in a range of 5 - 80 weight percent, preferably 20 - 80 weight percent, in wettable powders, 5 - 70 weight percent, preferably 10 - 50 weight percent, in emulsifiable concentrates, and 0.5 - 20 weight percent, preferably 1 - 10 weight percent in dust formulations.
Incidentally, wettable powder or emulsifiable concentrate containing proper quantity of the active compound is suspended or emulsified in water and then sprayed to the foliages of the plants or to the soil around the cultivated plants. Furthermore, the compounds may be used as a mixture with other fungicides, insecticides, acaricides and herbicide.
Some examples in this invention are stated below. But the main compounds and the additives are not defined limitedly by these Examples.
EXAMPLE 6. Wettable Powder 
______________________________________                                    
               Parts by weight                                            
______________________________________                                    
Compound No. 1   40                                                       
Sodium alkylsulfonate                                                     
                  7                                                       
Diatomaceous earth                                                        
                 53                                                       
______________________________________
These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 40% of the active ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.
EXAMPLE 7. Emulsifiable Concentrate 
______________________________________                                    
                  Parts by weight                                         
______________________________________                                    
Compound No. 2      30                                                    
Polyoxyethylenealkylarylether                                             
                     8                                                    
Xylene              42                                                    
Dimethylformamide   20                                                    
______________________________________
These are mixed and dissolved. Consequently, emulsifiable concentration containing 30% of the active ingredient is obtained. In practical use, it is diluted to certain concentration with water and then is sprayed as an emulsion.
EXAMPLE 8. Dust Formulation 
______________________________________                                    
             Parts by weight                                              
______________________________________                                    
Compound No. 3 10                                                         
Talc           90                                                         
______________________________________
These are mixed homogeneously, reduced to fine particles. Consequently, dust formulation containing 10% of the active ingredient is obtained. In practical use, it is directly applied.
The superior fungicidal activity of compounds of this invention is clearly illustrated by the following tests.
Test 1. Test for Control of Alternaria leaf spot
Apple leaves were cut off from the potted apple plant (variety: starking) and the detached leaves were immersed during 30 to 60 seconds into the diluted solution of a specified concentration of wettable powder containing test compound.
After air-drying, the leaves were inoculated with the spore suspension of Alternaria mali in the concentration of 200,000/ml and incubated in a wet chamber at 28°C.
One day after innoculation, an average number of lesions was examined and evaluation of percent disease control was calculated on the basis of number of lesions occuring on the untreated check.
The state of preventing against the germinating of spore on leaves was also observed through a microscope. The result was shown in Table 2.
                                  Table 2                                 
__________________________________________________________________________
         Concentration of                                                 
                         State of inhibition                              
         active ingredient                                                
                   Control                                                
                         of spore                                         
Test Compound                                                             
         (ppm)     Value (%)                                              
                         germination*                                     
__________________________________________________________________________
4        250       100   +                                                
         125       100   +                                                
          63       90    ±                                             
5        250       80    ±                                             
         125       75    -                                                
          63       75    -                                                
6        250       100   ±                                             
         125       90    -                                                
          63       80    -                                                
11       250       80    ±                                             
         125       40    -                                                
          63       30    -                                                
Captafol**                                                                
         800       100   +                                                
         400       100   +                                                
         200       100   +                                                
         100       80    +                                                
Untreated                                                                 
         --         0    -                                                
__________________________________________________________________________
 *degree for state of inhibiton of spore germination:                     
  -: normal germination                                                   
  ±: abnormal germination                                              
  +: inhibition of spore germination                                      
 **cis-N[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,3-dicarboximide
Test 2. Pot Test for Control of Alternaria leaf spot
The potted young apple plants (Star King) were sprayed, at a rate of 100 ml. per plant, with an aqueous suspension having a concentration of 500, 250 and 125 ppm of an active ingredient which suspension was prepared by diluting a wettable powder with water to a specified concentration. Young branches having about 7 to 8 leaves were cut off from each tree and leaves were also cut off from tree after allowing to stand for 1 day, 3 days and 7 days in green-house after the spraying of above suspension, and then inoculated with spore suspension of Alternaria mali, and held under the condition of incubation for 24 hours in a wet chamber. Then, average number of lesions per branch was counted and evaluation of percent disease control was calculated on the base of number of lesions occuring on the untreated check. The state of inhibition of the spore germination was also observed.
                                  Table 3                                 
__________________________________________________________________________
      Concentra-                                                          
      tion of                                                             
            Control Value (%)                                             
      active in-                                                          
            Time between spraying and inoculation (days)                  
Test  gredient                                                            
            Detached branch                                               
                        Leaf                                              
Compound                                                                  
      (ppm) 1   3   7   1    7                                            
__________________________________________________________________________
      500   95  100 100 80+  95+                                          
4     250   80  90  70  80±                                            
                             85+                                          
      125   85  85  80  80±                                            
                             70±                                       
      500   89  90  98  75±                                            
                              80˜±                               
6     250   74  87  50  73-  78±                                       
      125   81  81  66  70-  63-                                          
Polyoxnes*                                                                
       50   100 100 100 100+ 100+                                         
Captafol**                                                                
      800   100 100 100 100+ 100+                                         
Untreated                                                                 
      --     0   0   0   0-   0-                                          
__________________________________________________________________________
 *A series of antibiotic substances produced in culture solution of a     
 Japanese Streptomyces species.                                           
 **cis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,3-dicarboximide.
Test 3. Test for Control of Late blight
Tomato leaves were cut off form the potted tomato (variety: Oogatafukuju) and the detached leaves were immersed during 30 to 60 seconds into the diluted solution of a specified concentration of wettable powder containing test compound. After air-drying, the leaves were inoculated with the zoospore suspension of late blight (Phytophthora capsici) in the concentration of 30,000/ml and incubated in a green-house at 28°C. 2 days after inoculation, the disease degree was examined and evaluation of percent disease control was calculated on the disease degree of untreated check. The results were shown in Table 4.
              Table 4                                                     
______________________________________                                    
           Concentration of                                               
           active ingredient                                              
                          Control Value                                   
Test compound                                                             
           (ppm)          (%)                                             
______________________________________                                    
1          500            100                                             
           250             98                                             
           125             71                                             
2          500            100                                             
           250             97                                             
           125             95                                             
3          500             91                                             
           250             28                                             
4          250            100                                             
           125            100                                             
            63             95                                             
5          250            100                                             
           125            100                                             
            63             30                                             
6          250            100                                             
           125            100                                             
            63             84                                             
11         250            100                                             
           125            100                                             
            63             95                                             
Captan*    250            100                                             
           125            100                                             
            63            100                                             
Untreated  --              0                                              
______________________________________                                    
 *cis-N-[(trichloromethyl)thio]-4-cyclohexene-1,3-dicarboximide
Test 4. Test for Control of Late blight
Seeds of tomato (variety: Oogatafukuju) were planted in a pot and cultivated for 2 weeks in a green-house.
When cotyledons developed or leaves began to develop,45 ml of an aqueous suspension prepared by diluting a wettable powder with water to a specified concentration was sprayed on the pot where 20 tomatoes seedlings were growing up. After the pot was placed in a green-house for 3 days, tomatoes were inoculated with the zoospore suspension of late blight (Phytophthora capsici) in the concentration of (30,000/ml) and incubated in a wet chamber at 28°C.
Three days after inoculation, the disease degree was examined an evaluation of percent disease control was calculated on the base of the disease degree on the untreated check.
Each test was repeated three times for each concentration. The average results were shown in Table 5.
              Table 5                                                     
______________________________________                                    
               Concentration of                                           
                             Control                                      
               active ingredient                                          
                             Value                                        
Test compound  (ppm)         (%)                                          
______________________________________                                    
1              500           93.9                                         
               250           89.6                                         
2              500           98.5                                         
               250           95.2                                         
4              500           100                                          
               250           100                                          
5              500           100                                          
               250           93.1                                         
6              500           100                                          
               250           100                                          
11             500           100                                          
               250           92.9                                         
Captan         250           100                                          
(50% wettable powder)                                                     
               125           98.2                                         
Untreated      --            0                                            
______________________________________
Test 5. Pot test for Control of Late blight
A tomato seedling (height: 45 - 50 cm, leaves: 15 - 20) was grown in a pot.
60 ml of an aqueous suspension prepared by diluting a wettable powder with water to a specified concentration was sprayed on the two pot and these pots were allowed to stand in a green-house.
5 days after spraying, tomato seedlings were inoculated with the zoospore suspension of late blight and incubated in a wet chamber at 28°C.
Three days after inoculation, the disease degree was examined and evaluation of percent disease control was calculated on the base of the disease degree on the untreated check. The results were shown in Table 6.
              Table 6                                                     
______________________________________                                    
        Concentration                                                     
Test    of active   Degree of disease*                                    
                                    Phyto-                                
compound                                                                  
        ingredient  leaf       stem   toxicity                            
______________________________________                                    
2       500         - ˜ ±                                        
                               -      none                                
4       500         -          -      none                                
Captan  250         - ˜ ±                                        
                               -      none                                
Untreated                                                                 
        --          ++ ˜ ++++                                       
                               ± ˜ ++                            
                                      none                                
______________________________________                                    
 *Degree of disease                                                       
 leaf                                                                     
 -: healthy                                                               
 ±- disease below 5%                                                   
 +: disease below 20%                                                     
 ++: disease below 40%                                                    
 +++: disease below 60%                                                   
 ++++: disease beyond 60%                                                 
 stem                                                                     
 -: healthy                                                               
 ±: disease of petiole                                                 
 +: disease of stem                                                       
 ++: disease of middle of stem
It is to be observed therefore that the present invention provides for a compound of the formula ##SPC5##wherein R1 is selected from the group consisting of straight or branched chain alkyl of 1 to 12 carbon atoms, alkenyl of 3 to 4 carbon atoms, propargyl, methoxyethyl, alkyl of 2 to 4 carbon atoms substituted with one or two chlorine or bromine atoms and cyclohexyl. Within this group the invention also provides for compounds in which R1 is alkyl of 4 to 5 carbon atoms. Compounds in which R1 is straight or branched chain alkyl of 1 to 12 carbon atoms, lower alkenyl or lower alkynyl are also provided for in the present invention.

Claims (13)

1. A compound of the formula ##SPC6##
wherein R1 is selected from the group consisting of
straight or branched chain alkyl of 1 to 12 carbon atoms,
alkenyl of 3 to 4 carbon atoms, propargyl, methoxyethyl,
alkyl of 2 to 4 carbon atoms substituted with one or two chlorine or
2. A compound of the formula ##SPC7##
wherein R1 is selected from the group consisting of
straight or branched chain alkyl of 1 to 12 carbon atoms, lower alkenyl and
3. A compound of the formula ##SPC8##
6. A fungicidal composition for plants comprising an inert carrier and a
7. A fungicidal composition for plants comprising an inert carrier and a
8. A fungicidal composition for plants comprising an inert carrier and a
9. A fungicidal composition for plants comprising an inert carrier and a
10. A fungicidal composition for plants comprising an inert carrier and a
11. A method of preventing injury to plants due to fungi comprising applying to the locus to be protected an effective amount of the compound
12. A method of preventing injury to plants due to fungi comprising applying to the locus to be protected an effective amount of the compound
13. A method of preventing injury to plants due to fungi comprising applying to the locus to be protected an effective amount of the compound
14. A method of preventing injury to plants due to fungi comprising applying to the locus to be protected an effective amount of the compound
15. A method of preventing injury to plants due to fungi comprising applying to the locus to be protected an effective amoutn of the compound of claim 5.
US05/599,664 1974-08-09 1975-07-28 Imidazole derivatives Expired - Lifetime US3983241A (en)

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DE (1) DE2535512A1 (en)
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WO2011104540A1 (en) * 2010-02-24 2011-09-01 Generics [Uk] Limited One step process for the preparation of capecitabine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1459782A (en) * 1964-05-27 1966-11-25 Fisons Pest Control Ltd Physiologically active composition containing substituted benzimidazoles for agricultural use
US3770764A (en) * 1971-05-25 1973-11-06 Du Pont 2-substituted-4,5-dicyanoimidazoles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1459782A (en) * 1964-05-27 1966-11-25 Fisons Pest Control Ltd Physiologically active composition containing substituted benzimidazoles for agricultural use
US3770764A (en) * 1971-05-25 1973-11-06 Du Pont 2-substituted-4,5-dicyanoimidazoles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Noller Chemistry of Organic Compounds 2nd ed. p. 244 Philadelphia, Saunders, 1957. *

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FR2281360A1 (en) 1976-03-05
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DE2535512A1 (en) 1976-02-19
IL47836A0 (en) 1975-10-15

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